KR20140137335A - Silicone composition that can be cross-linked by means of dehydrogenative condensation in the presence of a carbene-type catalyst - Google Patents

Abstract

The present invention relates to a silicone composition comprising components with ≡SiH / ≡SiOH groups, wherein the composition can be polymerized / crosslinked via a dehydrogenation condensation reaction in the presence of a solution type carbene-type catalyst.

Description

TECHNICAL FIELD The present invention relates to a silicone composition which can be crosslinked by a dehydrogenation condensation reaction in the presence of a carbene-type catalyst. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone composition capable of being crosslinked by a dehydrogenation condensation reaction in the presence of a carbene-

The present invention relates to the field of catalysis of the dehydrogenation condensation reaction which enables polymerization / crosslinking of silicon. The reactive species used are monomers, oligomers, and / or polymers of polyorganosiloxane nature.

The reaction units associated with these species are ≡SiH units and ≡SiOH units. As a result of the dehydrogenation reaction between these reactive silicone units, the ≡Si-O-Si≡ bond is formed and hydrogen gas is released.

The dehydrogenation condensation reaction is preferably carried out in the polymerization / crosslinking reaction paths known in the silicon field, that is, the polymerization route by reaction between ≡SiH unit and ≡Si-alkenyl (vinyl) unit, ≡SiOR unit and ≡SiOR unit (R = Alkyl) is an alternative to the polycondensation pathway. As a result of both these polymerization / crosslinking pathways, some degree of polymerized and to some degree crosslinked silicone products are produced which are used in many applications such as adhesives, sealing products, pointing products, adhesive primers, release coatings, Can be used to configure products.

According to French Patent FR-B-1 209 131, chloroplatinic acid (H ₂ PtCl ₆ .6H ₂ O) reacts with silanol Ph ₂ Si (OH) ₂ and the organosiloxane [(Me ₂ HSi) ₂ O] = Methyl, and Ph = phenyl), can catalyze the reaction by dehydrogenation condensation.

It is also possible to use rhodium complexes such as RhCl ₃ [(C ₈ H ₁₇ ) ₂ S] ₃ ), platinum complexes (such as Karstedt catalysts) or platinum, rhodium It is well known practice to use metal catalysts based on palladium or iridium. To iridium-based catalyst, there may be mentioned the following compounds: IrCl (CO) (TPP) 2, Ir (CO) 2 (acac), IrH (Cl) 2 (TPP) 3, [IrCl ( cyclooctene) ₂ ] ₂ , IrI (CO) (TPP) ₂ and IrH (CO) (TPP) _{3 wherein} TPP represents a triphenylphosphine group and acac represents an acetylacetonate group.

Other examples are catalysts such as amines, colloidal nickel or dibutyltin dilaurate (see Noll, "Chemistry and technology of silicones ", 205, Academic Press, 1968-2nd edition). However, although alkyltin-based catalysts are very effective, usually colorless liquids and can be dissolved in silicone oil, they have the disadvantage of toxicity (CMR2 reproductive toxicity).

Other catalysts are described in French patent application FR-A-2 06 930 for boron derivatives of the tris (pentafluorophenyl) borane type.

US-B-4 262 107 discloses a composition comprising a polydimethyldisiloxane containing a silanol end, a crosslinking agent comprising a polyorganosiloxane containing a? IH unit and a trimethylsilyl end and a rhodium complex (RhCl ₃ [(C ₈ H ₁₇ ) ₂ S] ₃ ). The silicone composition, which can be crosslinked by a dehydrogenation reaction carried out in the presence of a rhodium complex, can be used to prepare a release coating on a flexible support or metal film, such as paper and plastic. The crosslinking reaction is carried out at a temperature of 150 캜.

European patent application EP-A-1 167 424 discloses a process for the preparation of polydimethylsiloxane containing a silanol end and a polyorganosiloxane containing an aromatic group and ≡SiH end based on platinum, rhodium, palladium or iridium- In the presence of a metal catalyst capable of being subjected to a dehydrogenation condensation reaction to obtain a linear silicone block copolymer

French patent application FR-A-2 806 930 discloses a thermoactivatable catalyst for dehydrogenation condensation between a polyorganosiloxane containing ≡SiH units and a polyorganosiloxane containing ≡SiOH end units, such as tris (pentafluoro Phenyl) borane type boron derivatives. Such a silicone composition, which can be crosslinked by a dehydrogenation reaction carried out in the presence of a boric derivative type of Lewis acid, is useful for the preparation of flexible supports, in particular for release coatings on paper, and for crosslinking to control the quality of the crosslinking network It can also be used for the production of silicone foam.

The investigation of the prior art about the catalysis of the dehydrogenation condensation reaction between a polyorganosiloxane containing a siloxane ≡SiOH unit and a polyorganosiloxane containing a siloxane ≡SiH unit reveals that,

1) discover new non-toxic catalysts,

2) lowering the catalyst activation temperature,

3) the need to limit addition reactions is serious.

Patent application FR 03 41232 relates to a process for preparing a polyorganosiloxane by polymerization via ring opening and / or redistribution of the polyorganosiloxane in the presence of a catalyst (or initiator) composed of at least one nucleophilic carbene .

Patent application FR 06 03563 relates to a process for the polycondensation reaction of a polyorganosiloxane between at least one ≡SiOH unit and at least one ≡SiOR unit using a catalyst having a carbene structure

However, the carbene catalysts described in the above-mentioned two applications are unstable and generally have to be used in crystalline form or generated in situ from precursor salts. Unfortunately, carbenes are highly reactive species that decompose in open air, which means that they must be stored and handled under an inert atmosphere.

Thus, one of the objects of the present invention is to provide a novel, novel, and novel process which is stable in the open state for several months and can therefore be easily transported, thus facilitating industrial use without additional steps for on- There is provided a silicone composition comprising a component having an ≡SiH group and a ≡SiOH group which can be polymerized / crosslinked through a dehydrogenation reaction in the presence of a catalyst composition.

A further object of the present invention is to provide a novel non-toxic catalyst for the dehydrogenation polycondensation reaction of organopolysiloxanes having ≡SiH groups and ≡SiOH groups, which catalysts are particularly useful for the preparation of catalysts for synthesis and / Or purification steps by sublimation at very low yields, there is no restriction on the catalysts of the prior art with carbene structures, which makes it less expensive to synthesize.

Another object of the present invention is to provide a method of polymerizing and / or crosslinking a composition of the type mentioned when explaining the above objects, which method should be fast, economical and effective in terms of the quality of the final product obtained do.

It is a further object of the present invention to provide a method of producing at least one coating on a support, preferably a flexible support, comprising using the above-mentioned crosslinking / polymerization methods and compositions.

Another object of the present invention is a method of producing one or more articles made of a crosslinked silicone foam, comprising the steps of using the above-mentioned crosslinking / polymerization method and / or the above-mentioned composition when describing the objects. This method makes it possible to control the volume of the hydrogen gas to be discharged and the quality of the elastomer to be formed.

The term "elastomer" is used in the meaning given in the silicon field, and it is to be understood that it expresses the product obtained after the curing of the silicone composition, excluding all implied meaning related to its elasticity characteristic.

In order to achieve this object, it is entirely surprising and unexpected that the Applicant has found that the use of stable carbenes in alcoholic solutions makes it possible to obtain organopolysiloxane dehydrogenation condensation products for the polymerization of elastomeric compositions, for example silicone foams, And can catalyze the reaction.

Thus, the present invention firstly relates to a siloxane composition X that can be polymerized or crosslinked by a dehydrogenation condensation reaction, wherein said composition X is

At least one organosiloxane monomer, oligomer and / or polymer B having at least one? SiH reaction unit per molecule;

At least one organosiloxane monomer, oligomer and / or polymer C having at least one? SiOH reaction unit per molecule;

- a catalyst composition Y 'comprising:

a) a catalytically effective amount of at least one carbene polycondensation catalyst A of formula (I)

(In the formula,

X is -O-, -S-, -N (R) - and -P (R) - (R is C ₁ -C ₃₀ And the like, and the like,

- the same or different R ¹ , R ² and R ³ are optionally substituted C ₁ -C ₃₀ groups optionally comprising one or more atoms selected from the group consisting of S, P, Si, N and O,

- X, R ¹ , R ² and R ³ may be paired to form a 5-, 6- or 7-membered ring)

b) at least one solvent comprising at least one alcohol G

Optionally at least one polyorganosiloxane resin D; And

- optionally one or more fillers E

.

The catalyst composition Y 'for the polycondensation reaction by dehydrogenation condensation, which is used according to the present invention, is particularly effective and economical in view of the platinum catalyst.

One of the advantages of the dehydrogenation condensation processes presented herein is the use of a catalyst composition Y 'comprising at least one carbene which is stable in solution form at 20 < 0 > C.

Preferably, the catalyst composition consists solely of at least one alcohol G and the polycondensation catalyst A according to the invention. Alcohol G is present in a proportion of not less than 50% by weight, preferably not less than 55% by weight, based on the total weight of the catalyst composition Y ', more preferably not less than 60% by weight, based on the total weight of the catalyst composition Y' Is present in the catalyst composition Y '.

A process for preparing a catalyst composition Y '(stable carbene in the dissolved state in a solvent containing at least one alcohol G) is described in patent application FR 10 50108. The method comprises selectively deprotonizing the precursor salt using at least one strong base in situ to produce carbene, wherein the deprotonation is carried out in a solvent comprising one or more alcohols

More specifically, the process for preparing the catalyst composition Y '

a) optionally at least one strong base produced in situ, preferably at a temperature of from < RTI ID = 0.0 > 0 C <

(In the formula,

X is -O-, -S-, -N (R) - and -P (R) - (R is C ₁ -C ₃₀ Etc.), and the like,

- the same or different R ¹ , R ² and R ³ are optionally substituted C ₁ -C ₃₀ groups optionally comprising one or more atoms selected from the group consisting of S, P, Si, N and O,

- X, R ¹ , R ² and R ³ may be paired to form a 5-, 6- or 7-membered ring)

Of at least one carbene precursor compound A 'of formula (I), which is a salt containing an iminium group,

A strong base selected to enable deprotonation of hydrogen in the iminium group of formula (I '), and

- a solvent that is an alcohol or alcohol mixture

Under the above-mentioned conditions.

Advantageously, such deprotonation is carried out at room temperature (20 < 0 > C).

Preferably, compound A 'is selected from compounds of general formula (III) or (III'):

In the formula,

A and B independently represent a carbon or nitrogen atom,

In the formula (III), when A represents a nitrogen atom, T ₄ does not exist, and when B represents a nitrogen atom, T ₃ does not exist;

In the formula (III '), when A represents a nitrogen atom, T ₄ Or T _{4 '} is absent, and when B represents a nitrogen atom, T ₃ Or T < ₃ > is not present,

- T ₃ , T _{3 '} , T ₄ and T _4' independently of one another represent a hydrogen atom; Or cycloalkyl substituted with alkyl, optionally an alkyl or alkoxy group, aryl, alkenyl, alkynyl, and arylalkyl optionally substituted with an alkyl or alkoxy group (wherein the aryl moiety is optionally substituted with an alkyl or alkoxy group) Lt; / RTI >

T ₃ and T ₄ can form an aryl together with A and B when A and B each represent a carbon atom, in which case T _{3 '} And T < ₄ > are not present;

T ₁ and T ₂ are independently

1) alkyl, cycloalkyl optionally substituted with alkyl, alkyl which is perfluorinated or optionally substituted by perfluoroalkyl, optionally cycloalkyl substituted by alkyl or alkoxy, aryl optionally substituted by alkyl or alkoxy, alkenyl , Alkynyl, and arylalkyl (wherein the aryl moiety is optionally substituted with an alkyl or alkoxy group); or

2) a monovalent radical of formula (IV)

-V1-V2 (IV)

(In the formula,

V 1 is an optionally substituted, saturated or unsaturated divalent hydrocarbon group, preferably linear or branched C ₁ -C ₁₀ alkylene,

V2 is a monovalent group selected from the group consisting of the following substituents;

Alkoxy, -OR ^a (R ^a corresponds to ^a hydrogen atom, an alkyl group or an aryl group);

◆ _{^{silyl, -Si (OR b) x (}} R c) 3-x (R b groups are the hydrogen atom, an alkyl group, a silyl group or a siloxy sanil, R ^c groups are the alkyl group or an aryl group, x is 0, 1 , 2 or 3); And

An amine, preferably -N (R ^a ) ₂ (R ^a corresponds to ^a hydrogen atom, an alkyl group or an aryl group)

When the substituents T ₁ , T ₂ , T ₃ , T _{3 ' ,} T ₄ and T _4' are located on two adjacent ring members in the formulas (III) and (III ' To form a saturated or unsaturated hydrocarbon-based chain;

-Z < 1 > is, independently,

● -COOH of formula G ^o (G ^o is alkyl, advantageously C ₁ -C ₂₂ alkyl, or aryl, advantageously represents a C ₆ -C ₁₈ aryl which is optionally substituted with one or more C ₁ -C ₆ alkyl) Carboxylic acid;

Sulfonic acids of the formula G ^o -SO ₃ H (G ^o is as defined above);

Phosphoric acid of the formula G ^o -PO ³ H (G ^o is as defined above);

The following inorganic acids: HF, HCl, HBr, HI, H ₂ SO ₄ , H ₃ PO ₄ , HClO ₄ and HBF ₄ alone or a combination of these; And

● Mixture of these

Preferably an anion derived from selected Bronsted acid (a positive asset) in the group consisting of < RTI ID = 0.0 >

With respect to salt (III), the anion Z ₁ ^- is an anion derived from an organic or inorganic Bronsted acid (a positive asset). Usually, the anion Z ₁ ^- is derived from an acid less than pKa 6. Preferably, Z < _{1 >} ^- is derived from an acid less than pKa4, more preferably less than 2. The associated pKa value is the pKa value of the acid measured in water.

Examples of acids include those of the formula G ^o -COOH wherein G ^o is an alkyl group, for example a (C ₁ -C ₂₂ ) alkyl group, or an optionally substituted alkyl group, preferably one or more (C ₁ -C ₆ ) , a carboxylic acid of the aryl group, for example (C ₆ -C ₁₈₎ represents an aryl group); Sulfonic acids of the formula G ^o -SO ₃ H (G ^o is as defined above); And phosphonic acids of the formula G ^o -PO ₃ H (G ^o is as defined above), and other acids include HF, HCl, HBr, HI, H ₂ SO ₄ , H ₃ PO ₄ , HClO ₄ and HBF There are _four .

Preferred examples of the carboxylic acid are acetic acid, benzoic acid and stearic acid. An example of a preferred sulfonic acid may be benzenesulfonic acid, and an example of a preferred phosphonic acid may be phenylphosphonic acid.

The anion Z ₁ ^- derived from HCl, HI, HBF ₄ and HPF ₆ is more particularly preferred.

Thus, particularly preferred anions Z ₁ ^- are anions of halides, tetrafluoroborates and hexafluorophosphates.

Some examples of imidazolium salts are given below:

These consumable materials are readily available or readily prepared from commercially available compounds by those skilled in the art.

A method for the synthesis of a salt of formula (III) (wherein A = B = C) is described in US-B-5 077 414.

The method comprises, in the presence of a suitable acid,

(V)

(In the formula, T ₃ and T ₄ are as defined above) α- dicarbonyl a biotinylated compound HCHO) and (T ₁ -NH ₂ of And T < ₂ > -NH < _{2 &} gt ;. T ₁ and T ₂ are as defined above.

The nature of the anion Z ₁ ^- in the salt of formula (III) depends on the acid used in this step. The acids which can be used are, for example, the acids listed above and the acids which derive Z < _{1 >} ^- .

Other processes for the preparation of salts of formula (III) are described in Chem. Eur. J., 1996, 2, No. 12, pp. 1627-1636 and Angew. Chem. Int. Ed. Engl., 1997, 36, 2162-2147.

The reaction for preparing carbenes used as catalysts is carried out in a solvent containing at least one alcohol G or a mixture of alcohols G to obtain a stable carbene in a state dissolved in an alcohol-based solution.

Preferably, this alcohol G has the formula R ^o OH (R ^o is the appropriate alkyl, cycloalkyl, aryl, alkenyl, alkynyl, arylalkyl, One of the silyl and siloxane group, and preferably R ^o in the solvent is methyl, Ethyl, propyl, and butyl.

In a preferred embodiment, for the reaction to synthesize carbenes in solution, the strong base is preferably selected from the group consisting of alkali metal and alkaline earth metal hydroxides, alkoxides, hydrides and amides, preferably CH ₃ ONa, potassium tert-butyl , KOH, NaOH, CH ₃ CH ₂ OMgOCH ₂ CH ₃ , and mixtures thereof.

According to one case, this strong base can be formed in situ, for example by adding sodium or sodium hydride or magnesium to the alcohol under consideration. In this way, alkoxides can be generated in situ.

Advantageously, as a result of the deprotonation, a salt precipitates and separates from the carbene solution, which can then be used as the catalyst composition Y 'in the process of the invention described below.

Preferably, the catalytic composition Y 'according to the present invention comprises a polycondensation catalyst A of formula (II) or (II'):

In the formula,

- A ₁ and A ₂ independently represent a carbon atom or a nitrogen atom,

1) In the formula (II), when A ₁ represents a nitrogen atom, T ₄ does not exist, and when A ₂ represents a nitrogen atom, T ₃ does not exist;

2) In the formula (II '), when A ₁ represents a nitrogen atom, T ₄ Or T ₄ 'is absent, and when A ₂ represents a nitrogen atom, T ₃ Or T < ₃ > is not present,

- T ₃ , T _{3 '} , T ₄ and T _4' independently represent a hydrogen atom; Or cycloalkyl substituted with alkyl, optionally an alkyl or alkoxy group, aryl, alkenyl, alkynyl, and arylalkyl optionally substituted with an alkyl or alkoxy group (wherein the aryl moiety is optionally substituted with an alkyl or alkoxy group) Lt; / RTI >

- T ₃ and T ₄ is, A ₁ and A case ₂ represent each a carbon atom, A may form an aryl group with ₁ and A _2, in this case, T _{3 'and} T _4' is that it does not exist, Understood;

When T ₁ , T ₂ , T ₃ , T _{3 '} , T ₄ and T _4' are located on two adjacent ring members in formulas (II) and (II '), Can form an unsaturated hydrocarbon chain;

- T < _{1 >} and T < ₂ >

1) alkyl, cycloalkyl optionally substituted with alkyl, alkyl which is perfluorinated or optionally substituted by perfluoroalkyl, optionally cycloalkyl substituted by alkyl or alkoxy, aryl optionally substituted by alkyl or alkoxy, alkenyl , Alkynyl, and arylalkyl (wherein the aryl moiety is optionally substituted with an alkyl or alkoxy group); or

2) a monovalent radical of formula (IV)

-V1-V2 (IV)

(In the formula,

- V 1 is an optionally substituted, saturated or unsaturated divalent hydrocarbon group, preferably linear or branched C ₁ -C ₁₀ alkylene,

- V2 is a monovalent group selected from the group consisting of the following substituents;

-Alkoxy, -OR < ^a > (R ^a corresponds to ^a hydrogen atom, an alkyl group or an aryl group);

- _{^{silyl, -Si (OR b) x (}} R c) 3-x (R b groups are the hydrogen atom, an alkyl group, a silyl group or a siloxy sanil, R ^c groups are the alkyl group or an aryl group, x is 0, 1 , 2 or 3); And

-Amine, preferably -N (R ^a ) ₂ (wherein R ^a is a hydrogen atom, an alkyl group or an aryl group)

.

The term "alkyl" preferably refers to a linear (preferably linear) alkyl group containing from 1 to 10 carbon atoms, for example from 1 to 8 carbon atoms, even more preferably from 1 to 7 carbon atoms, Or branched saturated hydrocarbon chain.

Examples of alkyl groups are especially methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, n-pentyl, isoamyl and 1,1-dimethylpropyl. The alkyl portion of the alkoxy group is as defined above.

An alkyl group which is perfluorinated or optionally substituted by a perfluoroalkyl group preferably corresponds to the formula:

In the formula, p represents 0, 1, 2, 3 or 4, q is an integer from 1 to 10, C _q F _{2q + 1} is linear or branched. Preferred examples of these groups include - (CH ₂ ) ₂ - (CF ₂ ) ₅ -CF ₃ and - (CF ₂ ) ₇ -CF ₃ .

The term "aryl" refers to a monocyclic or polycyclic, preferably monocyclic or bicyclic aromatic hydrocarbon group having 6 to 18 carbon atoms. Within the scope of the present invention, the term "polycyclic aromatic group" means a group having two or more aromatic rings condensed with each other (ortho-condensed or ortho- and peri-condensed) Quot; is intended to mean a group having < RTI ID = 0.0 >

The aromatic hydrocarbon group ("aryl") may be, for example, one or more C ₁ -C ₃ alkyl, one or more halogenated hydrocarbon groups such as CF ₃ , one or more alkoxy groups such as CH ₃ O, optionally substituted with one or more hydrocarbon-based group containing one or more ketone units (e.g., CH ₃ CO-).

Examples of aryl include phenyl, naphthyl, anthryl and phenanthryl radicals.

The term "arylalkyl" refers to an alkyl group as defined above substituted on its hydrocarbon chain with one or more aryl groups, wherein the aryl group is as defined above. Examples include benzyl and triphenylmethyl.

The term "cycloalkyl" is intended to mean a monocyclic or polycyclic, preferably monocyclic or bicyclic, saturated hydrocarbon group having from 3 to 10 carbon atoms, even more preferably from 3 to 8 carbon atoms. The term "polycyclic saturated hydrocarbon group" is intended to mean a group in which two or more cyclic rings are attached to each other via s bonds and / or are condensed in pairs. Examples of polycyclic cycloalkyl groups are adamantine and norbornene. Examples of monocyclic cyclic groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

The term "alkenyl" is intended to mean a substituted or unsubstituted, linear or branched, unsaturated hydrocarbon chain having one or more olefinic double bonds, more preferably only one double bond. Preferably, the alkenyl group has from 2 to 8 carbon atoms, even more preferably from 2 to 6 carbon atoms. Such a hydrocarbon chain optionally contains one or more heteroatoms such as O, N or S. Preferred examples of the alkenyl group are an allyl group and a homoallyl group.

The term "alkynyl ", according to the present invention, is intended to mean a substituted or unsubstituted, linear or branched, unsaturated hydrocarbon chain having at least one acetylene triple bond, more preferably only one triple bond. Preferably, the alkynyl group has 2 to 8 carbon atoms, even more preferably 2 to 6 carbon atoms. For example, acetylenyl groups and propargyl groups can be mentioned. Such a hydrocarbon chain optionally contains one or more heteroatoms such as O, N or S.

According to the present invention, the term "silyl" is intended to mean a linear or branched group containing at least one silicon atom. An example of a silyl group is a polydimethylsiloxane chain.

The carbenes of formulas (II) and (II ') may have two or more condensed rings. That is, at least two of T ₁ , T ₂ , T ₃ , T _{3 '} , T ₄ and T _4' located on two neighboring ring members together, preferably saturated, having 3 to 6 carbon atoms Or an unsaturated hydrocarbon chain. The expression "saturated or unsaturated hydrocarbon chain" is intended to mean a linear or branched hydrocarbon chain which may or may not have at least one unsaturated group of an olefinic double bond or an acetylene triple bond

With respect to the preferred embodiments of the formulas (II) and (II '), an embodiment wherein A ₁ = A ₂ = carbon atom in the given formula (II) is preferred.

Preferred meanings for T < _{1 >} and T < ₂ > in this formula (II)

-Alkyl, in particular n-propyl, n-pentyl or neopentyl (-CH ₂ -C (CH ₃ ) ₃ );

-Cycloalkyl, especially cyclopentyl, cyclohexyl or adamantyl;

-Alkenyl, in particular allyl _{(-CH 2 -CH = CH 2)} , methallyl _{(-CH 2 -C (CH 3)} = CH 2);

-Alkynyl, especially propargyl, homoproperitile (- (CH2) 2-C? H); or

- the monovalent group (V) defined above, in particular:

Also in formula (II), preferably T ₃ and T ₄ both correspond to hydrogen or together form aryl, more preferably phenyl.

As an example of carbenes, mention may be made of those listed in Table 2 on page 48 of "Bourissou et al., Chem. Rev., 2000, 100, 39-91".

The amount of the polycondensation reaction catalyst A according to the present invention may be 0.1 wt% to 10 wt%, preferably 0.1 wt% to 5 wt%, based on the total weight of the composition X according to the present invention.

Another subject of the present invention is a process for the preparation of polyorganosiloxanes comprising, on the one hand, one or more organosiloxane monomers, oligomers and / or polymers B having at least one? SiH reaction unit per molecule and, on the other hand, Consists of the use of at least one catalyst composition Y 'according to the invention, as defined herein, for the dehydrogenation of one or more organosiloxane monomers, oligomers and / or polymers C.

Preferentially, the organosiloxane monomer, oligomer and / or polymer B comprising the SiH reaction unit has at least one unit of the formula (VIII) shown below and has a unit of the formula (IV) at the end, or Is a cyclic entity consisting of units of formula (VIII): < RTI ID = 0.0 >

In the formula,

R ^1, which may be the same or different,

Is a linear or branched alkyl radical containing from 1 to 8 carbon atoms optionally substituted with one or more halogens, preferably fluorine, and the alkyl radicals are preferably methyl, ethyl, propyl, octyl and 3,3,3- Lt; / RTI > is trifluoropropyl,

An optionally substituted cycloalkyl radical containing from 5 to 8 carbon atoms in the cyclic structure,

An optionally substituted aryl radical containing from 6 to 12 carbon atoms, or

An aralkyl moiety having an alkyl moiety containing from 5 to 14 carbon atoms and an aryl moiety containing from 6 to 12 carbon atoms and an alkoxy moiety having from 1 to 3 carbon atoms in the aryl moiety, Lt; / RTI >

Z is similar or different

Represents a hydrogen radical, or

Represents an R ¹ group under the condition that two or more Z's per molecule represent a hydrogen atom;

According to a preferred embodiment, the organosiloxane monomer, oligomer and / or polymer C comprising ≡SiOH reaction units has at least one unit of the formula (IV) shown below, Or a cyclic moiety consisting of units of formula (IV):

In the formula,

- R ^2, which may be the same or different,

Is a linear or branched alkyl radical containing from 1 to 8 carbon atoms optionally substituted with one or more halogens, preferably fluorine, and the alkyl radicals are preferably methyl, ethyl, propyl, octyl and 3,3,3- Lt; / RTI > is trifluoropropyl,

An optionally substituted cycloalkyl radical containing from 5 to 8 carbon atoms in the cyclic structure,

An optionally substituted aryl radical containing from 6 to 12 carbon atoms, or

An aralkyl moiety having an alkyl moiety containing from 5 to 14 carbon atoms and an aryl moiety containing from 6 to 12 carbon atoms and an alkoxy moiety having from 1 to 3 carbon atoms in the aryl moiety, Lt; / RTI >

- Z 'are similar or different

Represents a hydroxyl group, or

Represents an R < ² > group provided that at least two Z 'per molecule represent a hydroxyl-OH group.

B and C type species also include structural units referred to as (Q) or (T) as defined below:

Wherein R < ³ > may represent one of the substituents suggested for R < ^{1 >} or R < ² >.

According to one advantageous variant of the invention, the polyorganosiloxane B used comprises from 1 to 50 siloxyl ≡SiH unit (s) per molecule.

According to one advantageous variant of the invention, the polyorganosiloxane C used comprises from 1 to 50 siloxyl ≡SiOH unit (s) per molecule.

Particularly preferred as derivatives B are organosiloxane monomers, oligomers and / or polymers B comprising ≡SiH reaction units corresponding to the general formula (VI)

In the formula,

- x and y each represent an integer or a fraction ranging from 0 to 200,

- R ' ¹ and R " ¹ are, independently of one another,

Is a linear or branched alkyl radical containing from 1 to 8 carbon atoms optionally substituted with one or more halogens, preferably fluorine, and the alkyl radicals are preferably methyl, ethyl, propyl, octyl and 3,3,3- Lt; / RTI > is trifluoropropyl,

An optionally substituted cycloalkyl radical containing from 5 to 8 carbon atoms in the cyclic structure,

An optionally substituted aryl radical containing from 6 to 12 carbon atoms, or

An aralkyl moiety having an alkyl moiety containing from 5 to 14 carbon atoms and an aryl moiety containing from 6 to 12 carbon atoms,

- R " ¹ can also be hydrogen, provided that the radical R" ¹ corresponds to hydrogen when x = 0.

Particularly preferred as derivatives C are organosiloxane monomers, oligomers and / or polymers C comprising ≡SiOH reaction units corresponding to the general formula (VII)

In the formula,

- x 'and y' each represent an integer or a fraction ranging from 0 to 1200,

- R ' ² and R " ² are, independently of one another,

Is a linear or branched alkyl radical containing from 1 to 8 carbon atoms optionally substituted with one or more halogens, preferably fluorine, and the alkyl radicals are preferably methyl, ethyl, propyl, octyl and 3,3,3- Lt; / RTI > is trifluoropropyl,

An optionally substituted cycloalkyl radical containing from 5 to 8 carbon atoms in the cyclic structure,

An optionally substituted aryl radical containing from 6 to 12 carbon atoms, or

An aralkyl moiety having an alkyl moiety containing from 5 to 14 carbon atoms and an aryl moiety containing from 6 to 12 carbon atoms,

- R " ² can also be OH, provided that the radical R" ² corresponds to OH when x '= 0.

The following compounds are very particularly preferred as the silicone derivative B of the present invention:

In the formula,

a, b, c, d, and e are numbers in the following ranges:

- in the polymer of formula S1:

0? A? 150, preferably 0? A? 100, preferably 0? A? 20,

1? B? 55, preferably 10? B? 55, preferably 30?

- in the polymer of formula S2:

0? C? 15,

- in the polymer of formula S3:

5? D? 200, preferably 20? D? 50,

2? E? 50, preferably 10? E30.

Very particular preference is given to compounds of the formula (S4) as the silicone derivatives C of the invention:

In the formula, 1? F? 1200, preferably 50? F? 400, and even more preferably 150? F? 250.

As long as the siloxane species B and C are oligomers or polymers, B and C can be described as specified below.

The polyorganosiloxane B may be linear (e.g., (VII)), branched or cyclic. For economic reasons, the viscosity of the polyorganosiloxane B is preferably less than 100 mPa.s; The organic radicals which may be the same or different are preferably methyl, ethyl and / or phenyl. When the polyorganosiloxane B is linear, the hydrogen atoms of the? SiH functional groups are directly bonded to the silicon atoms located in the terminal (s) and / or the chain in the chain.

As an example of linear component B, mention may be made of polymethylhydroxylsiloxanes including trimethylsiloxyl and / or hydrodimethylsiloxy end.

Among the cyclic polymers, mention may be made of compounds corresponding to the following formulas:

_{[OSi (CH 3) H]} 4; _{[OSi (CH 3) H]} 5; _{[OSi (CH 3) H]} 3; _{[OSi (CH 3) H]} 8; _{[OSi (C 2 H 5)} H] 3.

The viscosity of component C can reach 200,000 mPa.s. For economic reasons, a component whose viscosity is generally about 20 to 10,000 mPa.s is selected.

The same or different organic groups normally present in component C, alpha, omega -hydroxylated oils or gums are methyl, ethyl, phenyl and trifluoropropyl radicals. Preferably, at least 80% of the number of organic groups is a methyl group directly bonded to the silicon atom. In the context of the present invention, α, ω-bis (hydroxy) polydimethylsiloxanes are more particularly preferred.

The polyorganosiloxane C may be a resin. Resin C containing a silanol functional group, with one or more of, R'SiO _3/2 (T unit) and SiO _4/2 (Q units) units per molecule, R'SiO _1/2 (M units) and R ^_'2 SiO _^2/2 has one or more of the (D unit) units. Typical radicals R 'are methyl, ethyl, isopropyl, tert-butyl and n-hexyl. MQ ^{( OH )} , MDQ ^{( OH )} , TD ^{( OH )} and MDT ^{( OH )} resins may be mentioned as examples of resins.

In order to control the viscosity of the composition, it is also possible to use a solvent of the polyorganosiloxane B or C. Examples of such conventional solvents for silicone polymers include aromatic type solvents such as xylene and toluene; Saturated aliphatic solvents such as hexane, heptane, white-spirit ^占 tetrahydrofuran and diethyl ether; And chlorinated solvents, such as methylene chloride and perchlorethylene. However, in connection with the present invention, a solvent is preferably not used.

The molar ratio of ≡SiH / ≡SiOH is advantageously from 1 to 100, preferably from 10 to 50, even more preferably from 15 to 45.

The composition according to the invention may also comprise at least one polyorganosiloxane D. Such resins are well known and commercially available branched polyorganosiloxane oligomers or polymers. They are present in solution form, preferably in the form of a siloxane solution. These are, in their structure, the formula _{R '3 SiO 1/2 (} M _{units), R' 2 SiO 2/} 2 (D unit), R'SiO _3/2 (T unit) and SiO _4/2 (Q units) At least one of the units thus included is a T unit or a Q unit.

Radicals R 'are the same or different, linear or branched C ₁ -C ₆ An alkyl radical, a C ₂ -C ₄ alkenyl radical, a phenyl radical or a trifluoro-3,3,3-propyl radical.

For example, alkyl radicals R 'may refer to methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals; As the alkenyl radical R, a vinyl radical may be mentioned.

In the polyorganosiloxane resin D of the type mentioned above, it should be understood that some of the radicals R 'are alkenyl radicals.

Mention may be made, as examples of branched polyorganosiloxane oligomers or polymers D, of MQ resins, MDQ resins, TD resins and MDT resins, and alkenyl functionalities may be included in M, D and / or T units. An example of a particularly suitable -E-resin may refer to a vinylated MDQ or MQ resin having a vinyl group content of from 0.2% by weight to 10% by weight, and such vinyl groups are included in M and / or D units.

The resin D is advantageously present in a concentration of from 5 wt% to 70 wt%, preferably from 10 wt% to 60 wt%, even more preferably from 20 wt% to 60 wt%, based on all components in the composition.

The composition according to the invention may also contain filler E, which filler is preferably a mineral filler and is selected from siliceous or non-silicic materials. If the siliceous material is a problem, these materials may function as reinforcing fillers or semi-reinforcing fillers. The reinforcing siliceous filler is selected from colloidal silica, powders of fumed silica, powders of precipitated silica, or mixtures thereof.

The average particle size of these powders is generally less than 0.1 μm and the BET specific surface area is more than 50 m ² / g, preferably 100 to 300 m ² / g.

Semi-reinforcing siliceous fillers such as diatomaceous earth or fine quartz can also be used.

With respect to non-silicate mineral materials, these materials may be included as semi-reinforcing or bulk expanding mineral fillers. Examples of such non-silicate fillers which may be used alone or in admixture include carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, zirconium dioxide, zirconate, non-expanded vermiculite, calcium carbonate, zinc oxide, mica, , Iron oxide, barium sulfate, and slaked lime. The particle size of such a filler is generally from 0.001 to 300 μm and the BET specific surface area is less than 100 m ² / g.

In practice, but in a non-limiting manner, the filler used is silica.

Any suitable compatibilizer, specifically hexamethyldisilazane, can be used to treat the filler. For further details regarding this, see, for example, patent FR-B-2 764 894.

On a weight basis, the filler is used in an amount of 5% to 30%, preferably 7% to 20%, for all components used in the preparation.

Of course, depending on the intended end application, all kinds of additives may be used to enrich the composition.

Adhesion Control Systems on Flexible Supports (Paper or Polymer Film) Adhesion-regulating systems selected from among known systems may be included in the present compositions. French patent FR-B-2 450 642, US patent US-B-3,772,247 or European patent application EP-A-0 601 938.

Other functional additives of the present compositions may include bactericides, photosensitizers, fungicides, antiwear agents, antifreeze agents, wetting agents, defoamers, synthetic latexes, coloring agents or acidifying agents.

Among common additives are adhesion promoters, such as adhesives comprising at least one alkoxylated organosilane, at least one epoxidized organosilane compound, and at least one metal chelate and / or one metal alkoxide Mention may be made of accelerators, for example,

- vinyltrimethoxysilane or VTMO,

- glycidoxypropyltrimethoxysilane or GLYMO, and

- tert-butyl titanate or TBOT.

The composition may be a solution or an emulsion. In the latter case, the composition may comprise at least one surfactant, and optionally at least one pH-fixing agent, such as HCO ₃ ^- / CO ₃ ^{2 -} and / or H ₂ PO ₄ ^- / HPO ₄ ^{2 -} have.

According to another of its aspects, the present invention relates to a process for the polymerization and / or crosslinking of the siloxane composition X according to the invention as defined above, wherein a dehydrogenation reaction is carried out between the compound B and the compound C , And that the dehydrogenation condensation reaction is initiated by the catalyst composition Y 'as defined above.

For catalyst addition, at least two embodiments are possible.

The catalyst can be added, for example, to a mixture of compounds B and C, for example, to a mixture of polymer of type S1, S2 or S3 and polymer of type S4, or, preferably, , S4 type of polymer) with compound B (e.g., a polymer of S1, S2 or S3), the catalyst may be premixed with compound C.

Regardless of the variant discussed above, preferably the catalyst is used in the form of a solution dissolved in a solvent containing at least one alcohol.

Generally, the mixing step is carried out by stirring at room temperature.

The catalyst solution can be used, for example, to prepare a bath with the monomer (s), oligomer (s) and / or polymer (s) which are polymerized and / or crosslinked by a dehydrogenation condensation reaction, ) Is 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight in the bath.

The preparation of the silicone composition according to the invention, which can be used as a coating substrate for producing coatings with a particularly spontaneous properties, depends on whether the emulsion is used or not, with or without a solvent, Is carried out according to the known mixing method.

The present invention also relates to a method of producing one or more coatings on a support, preferably a flexible support, said method comprising essentially applying a siloxane composition X according to the invention as defined above to said support , Optionally activating the siloxane composition X to a temperature of at least 50 ° C, preferably from 50 ° C to 130 ° C, for example from 110 ° C to 130 ° C, followed by crosslinking the siloxane composition X.

According to the present method, the composition is applied to a flexible support or material through an apparatus used to coat paper on an industrial machine, such as a 5-roll coating head, an air knife system or an equilibrium bar system, To pass through a heated tunnel oven to a temperature of 130 占 폚, for example 100 占 폚 to 110 占 폚.

The composition may be applied to any flexible material or substrate such as various types of paper (super calendared paper, coated paper, glazinc paper), cardboard, cellulose sheet, metal sheet, plastic film (polyester, Etc.).

The amount of composition deposited is from about 0.5 to 2 grams per m ^{2 of} area to be treated, which corresponds to depositing from about 0.5 to 2 μm layers.

The coated material or support may then be contacted with any pressure sensitive rubber, acrylic or other adhesive material. The adhesive material can be easily separated from the support or material.

A flexible support coated with a release film can, for example,

An outer surface coated with a pressure sensitive adhesive layer and an outer surface including a silicone release coating;

A paper or polymer film for protecting the adhesive side of self-adhesive or pressure-sensitive adhesive elements; or

- Polymer films of the type of polyvinyl chloride (PVC), polypropylene, polyethylene or polyethylene terephthalate

Lt; / RTI >

Another subject of the present invention is a method of making one or more articles made of a crosslinked silicone foam, said method essentially comprising, under conditions for controlling the reaction to enable the formation of a silicone foam, The composition is preferably crosslinked using organosiloxanes B and C as defined above.

The compositions according to the invention are used in the field of optical fiber coating as well as in the field of release coatings on paints, encapsulation of electrical and electronic components and coatings for textiles.

The subject matter of the present invention is also any coating obtained by crosslinking and / or polymerizing the siloxane composition X according to the invention, as defined above. Such coatings may be varnishes, adhesive coatings, release coatings and / or coatings of the ink type.

The present invention also

Any article comprising at least one surface of which is coated with the above-mentioned thermally polymerized and / or crosslinked siloxane composition X; And

- a crosslinked silicone foam obtained by crosslinking the above-mentioned composition X

.

Example

Example  One:

4 g of an?,? - dihydroxylated polydimethylsiloxane oil having a viscosity of 100 mPa.s were mixed with 0.2 g of MD'nM oil having a viscosity of 20 to 25 mPa.s under magnetic stirring. The SiH / SiOH molar ratio was 1.4. 0.05 mmol (40 wt% carbene NHC-Cy _{2 in} ethanol) of carbene NHC-Cy ₂ [1,3- (dicyclohexyl) imidazolylidene] in the form of an ethanol solution was added in one step. In less than one minute, the mixture produced a foam that was four times larger than the initial volume.

Siloxyl units of _{M = (CH 3) SiO 1} /2

Siloxyl units _{D '= (CH 3) (} H) SiO 2/2

Claims (12)

Can be polymerized or crosslinked by a dehydrogenation condensation reaction,
At least one organosiloxane monomer, oligomer and / or polymer B having at least one? SiH reaction unit per molecule;
At least one organosiloxane monomer, oligomer and / or polymer C having at least one? SiOH reaction unit per molecule;
- a catalyst composition Y 'comprising:
a) a catalytically effective amount of at least one carbene polycondensation catalyst A of formula (I)

(In the formula,
X is -O-, -S-, -N (R) - and -P (R) - (R is C ₁ -C ₃₀ And the like, and the like,
- the same or different R ¹ , R ² and R ³ are optionally substituted C ₁ -C ₃₀ groups optionally comprising one or more atoms selected from the group consisting of S, P, Si, N and O,
- X, R ¹ , R ² and R ³ may be paired to form a 5-, 6- or 7-membered ring)
b) at least one solvent comprising at least one alcohol G
Optionally at least one polyorganosiloxane resin D; And
- optionally one or more fillers E
Containing
Siloxane composition X. The siloxane composition according to claim 1, wherein the catalyst A is a catalyst of the following formula (II) or (II '):

(In the formula,
- A ₁ and A ₂ independently represent a carbon atom or a nitrogen atom,
1) In the formula (II), when A ₁ represents a nitrogen atom, T ₄ does not exist, and when A ₂ represents a nitrogen atom, T ₃ does not exist;
2) In the formula (II '), when A ₁ represents a nitrogen atom, T ₄ Or T ₄ 'is absent, and when A ₂ represents a nitrogen atom, T ₃ Or T < ₃ > is not present,
- T ₃ , T _{3 '} , T ₄ and T _4' independently represent a hydrogen atom; Or cycloalkyl substituted with alkyl, optionally an alkyl or alkoxy group, aryl, alkenyl, alkynyl, and arylalkyl optionally substituted with an alkyl or alkoxy group (wherein the aryl moiety is optionally substituted with an alkyl or alkoxy group) Lt; / RTI >
- T ₃ and T ₄ is, A ₁ and A case ₂ represent each a carbon atom, A may form an aryl group with ₁ and A _2, in this case, T _{3 'and} T _4' is that it does not exist, Understood;
When T ₁ , T ₂ , T ₃ , T _{3 '} , T ₄ and T _4' are located on two adjacent ring members in formulas (II) and (II '), Can form an unsaturated hydrocarbon chain;
- T < _{1 >} and T < ₂ >
1) alkyl, cycloalkyl optionally substituted with alkyl, alkyl which is perfluorinated or optionally substituted by perfluoroalkyl, optionally cycloalkyl substituted by alkyl or alkoxy, aryl optionally substituted by alkyl or alkoxy, alkenyl , Alkynyl, and arylalkyl (wherein the aryl moiety is optionally substituted with an alkyl or alkoxy group); or
2) a monovalent radical of formula (IV)
-V1-V2 (IV)
(In the formula,
- V 1 is an optionally substituted, saturated or unsaturated divalent hydrocarbon group, preferably linear or branched C ₁ -C ₁₀ alkylene,
- V2 is a monovalent group selected from the group consisting of the following substituents;
-Alkoxy, -OR < ^a > (R ^a corresponds to ^a hydrogen atom, an alkyl group or an aryl group);
- _{^{silyl, -Si (OR b) x (}} R c) 3-x (R b groups are the hydrogen atom, an alkyl group, a silyl group or a siloxy sanil, R ^c groups are the alkyl group or an aryl group, x is 0, 1 , 2 or 3); And
-Amine, preferably -N (R ^a ) ₂ (wherein R ^a is a hydrogen atom, an alkyl group or an aryl group)
Lt; / RTI > The organosiloxane monomer, oligomer and / or polymer C as claimed in claim 1 or 2, wherein the organosiloxane monomer, oligomer and / or polymer C comprising the? SiOH reaction unit has at least one unit of the formula (IV) Or a cyclic structure moiety consisting of units of the formula (IV).

(In the formula,
- R ^2, which may be the same or different,
Is a linear or branched alkyl radical containing from 1 to 8 carbon atoms optionally substituted with one or more halogens, preferably fluorine, and the alkyl radicals are preferably methyl, ethyl, propyl, octyl and 3,3,3- Lt; / RTI > is trifluoropropyl,
An optionally substituted cycloalkyl radical containing from 5 to 8 carbon atoms in the cyclic structure,
An optionally substituted aryl radical containing from 6 to 12 carbon atoms, or
An aralkyl moiety having an alkyl moiety containing from 5 to 14 carbon atoms and an aryl moiety containing from 6 to 12 carbon atoms and an alkoxy moiety having from 1 to 3 carbon atoms in the aryl moiety, Lt; / RTI >
- Z 'are similar or different
Represents a hydroxyl group, or
R < ² > groups, provided that at least two Z 'per molecule represent a hydroxyl-OH group). 4. The composition according to any one of claims 1 to 3, characterized in that the organosiloxane monomer, oligomer and / or polymer B comprising ≡SiH reaction units corresponds to the following general formula (VI)

(In the formula,
- x and y each represent an integer or a fraction ranging from 0 to 200,
- R ' ¹ and R " ¹ are, independently of one another,
Is a linear or branched alkyl radical containing from 1 to 8 carbon atoms optionally substituted with one or more halogens, preferably fluorine, and the alkyl radicals are preferably methyl, ethyl, propyl, octyl and 3,3,3- Lt; / RTI > is trifluoropropyl,
An optionally substituted cycloalkyl radical containing from 5 to 8 carbon atoms in the cyclic structure,
An optionally substituted aryl radical containing from 6 to 12 carbon atoms, or
An aralkyl moiety having an alkyl moiety containing from 5 to 14 carbon atoms and an aryl moiety containing from 6 to 12 carbon atoms,
- R " ¹ can also be hydrogen, with the proviso that when x = 0, the radical R" ¹ corresponds to hydrogen. 5. The composition according to any one of claims 1 to 4, characterized in that the organosiloxane monomer, oligomer and / or polymer C comprising? SiOH reaction units correspond to the general formula (VII)

(In the formula,
- x 'and y' each represent an integer or a fraction ranging from 0 to 1200,
- R ' ² and R " ² are, independently of one another,
Is a linear or branched alkyl radical containing from 1 to 8 carbon atoms optionally substituted with one or more halogens, preferably fluorine, and the alkyl radicals are preferably methyl, ethyl, propyl, octyl and 3,3,3- Lt; / RTI > is trifluoropropyl,
An optionally substituted cycloalkyl radical containing from 5 to 8 carbon atoms in the cyclic structure,
An optionally substituted aryl radical containing from 6 to 12 carbon atoms, or
An aralkyl moiety having an alkyl moiety containing from 5 to 14 carbon atoms and an aryl moiety containing from 6 to 12 carbon atoms,
- R " ² can also be OH, with the proviso that when x '= 0, the radical R" ² corresponds to OH. On the one hand, at least one organosiloxane monomer, oligomer and / or polymer B with at least one? SiH reaction unit per molecule and at least one organosiloxane monomer with at least one? SiOH reaction unit per molecule The use of at least one catalyst composition Y 'as defined in claim 1 or 2 for dehydrogenation condensation between an oligomer and / A method for polymerizing and / or crosslinking the siloxane composition X according to any one of claims 1 to 5, wherein a dehydrogenation condensation reaction is carried out between the compound B and the compound C, Characterized in that it is initiated by the catalyst composition Y 'according to claim 1 or 2. A process for preparing one or more continuous or discontinuous coatings on a support, preferably a flexible support, essentially comprising applying the siloxane composition X defined in any one of claims 1 to 5 to the support And optionally activating the siloxane composition X to a temperature of at least 50 < 0 > C, after which the siloxane composition X can be crosslinked. A process for producing at least one article made of a crosslinked silicone foam, characterized in that the siloxane composition X defined in any one of claims 1 to 5 is crosslinked under conditions for controlling the reaction, . ≪ / RTI > A coating obtained by crosslinking and / or polymerizing the siloxane composition X as defined in any one of claims 1 to 5. An article comprising at least one surface of a solid material coated with a thermally polymerized and / or crosslinked siloxane composition as defined in any one of claims 1 to 5. A crosslinked silicone foam obtained by crosslinking the siloxane composition X as defined in any one of claims 1 to 5.

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